Size and shape evolution of pores in a viscoplastic matrix under compression

The frequent use of soils and earth materials for hydraulic capping and for geo‐environmental waste containment motivated our interest in detailed modelling of changes in size and shape of macro‐pores to establish links between soil mechanical behaviour and concurrent changes in hydraulic and transport properties. The objective of this study was to use finite element analysis (FEA) to test and extend previous analytical solutions proposed by the authors describing deformation of a single macro‐pore embedded in linear viscoplastic soil material subjected to anisotropic remote stress. The FEA enables to consider more complex pore geometries and provides a detailed picture of matrix yield behaviour to explain shortcomings of approximate analytical solutions. Finite element and analytical calculations agreed very well for linear viscous as well as for viscoplastic materials, only limited for the case of isotropic remote stress due to the simplifications of the analytical model related to patterns and onset of matrix‐yielding behaviour. FEA calculations were compared with experimental data obtained from a compaction experiment in which pore deformation within a uniform modelling clay sample was monitored using CAT scanning. FEA predictions based on independently measured material properties and initial pore geometry provided an excellent match with experimentally determined evolution of pore size and shape hence lending credence to the potential use of FEA for more complex pore geometries and eventually connect macro‐pore deformation with hydraulic properties. Copyright © 2006 John Wiley & Sons, Ltd.     

Ab initio infra-red spectra of iron-polycyclic aromatic hydrocarbon compounds: a model case

C₁₀H₆-Fe⁺ complexes were observed by Fourier transform mass spectrometry by Marty et al. (Chem. Phys. Lett. 256 (1996) 669). In this article, we present the infra-red (IR) spectra of the two isomers calculated by ab initio methods of quantum chemistry. In the past, the same approach has predicted successfully unexpected features of the IR spectra of polycyclic aromatic hydrocarbon (PAH) cations which were confirmed by measurements in matrices (J. Phys. Chem. 98 (1994) 9187). The C₁₀H₆-Fe⁺ systems are models for larger PAHs-Fe⁺ complexes, which are believed to play a key rôle in space chemistry.     

The stable isotope signature of kilometre-scale fracturedominated metamorphic fluid pathways, Mary Kathleen, Australia

Abstract Large calcite veins and pods in the Proterozoic Corella Formation of the Mount Isa Inlier provide evidence for kilometre-scale fluid transport during amphibolite facies metamorphism. These 10- to 100-m-scale podiform veins and their surrounding alteration zones have similar oxygen and carbon isotopic ratios throughout the 200 × 10-km Mary Kathleen Fold Belt, despite the isotopic heterogeneity of the surrounding wallrocks. The fluids that formed the pods and veins were not in isotopic equilibrium with the immediately adjacent rocks. The pods have δ¹³C_calcite values of –2 to –7% and δ¹⁸O_calcite values of 10.5 to 12.5%. Away from the pods, metadolerite wallrocks have δ¹⁸O_whole-rock values of 3.5 to 7%. and unaltered banded calc-silicate and marble wallrocks have δ¹³C_calcite of –1.6 to –0.6%, and δ¹⁸O_calcite of 18 to 21%. In the alteration zones adjacent to the pods, the δ¹⁸O values of both metadolerite and calc-silicate rocks approach those of the pods. Large calcite pods hosted entirely in calc-silicates show little difference in isotopic composition from pods hosted entirely in metadolerite. Thus, 100- to 500-m-scale isotopic exchange with the surrounding metadolerites and calc-silicates does not explain the observation that the δ¹⁸O values of the pods are intermediate between these two rock types. Pods hosted in felsic metavolcanics and metasiltstones are also isotopically indistinguishable from those hosted in the dominant metadolerites and calc-silicates. These data suggest the veins are the product of infiltration of isotopically homogeneous fluids that were not derived from within the Corella Formation at the presently exposed crustal level, although some of the spread in the data may be due to a relatively small contribution from devolatilization reactions in the calc-silicates, or thermal fluctuations attending deformation and metamorphism. The overall L-shaped trend of the data on plots of δ¹³C vs. δ¹⁸O is most consistent with mixing of large volumes of externally derived fluids with small volumes of locally derived fluid produced by devolatilization of calc-silicate rocks. Localization of the vein systems in dilatant sites around metadolerite/calc-silicate boundaries indicates a strong structural control on fluid flow, and the stable isotope data suggest fluid migration must have occurred at scales greater than at least 1 km. The ultimate source for the external fluid is uncertain, but is probably fluid released from crystallizing melts derived from the lower crust or upper mantle. Intrusion of magmas below the exposed crustal level would also explain the high geothermal gradient calculated for the regional metamorphism.     

Fluid infiltration during contact metamorphism of interbedded marble and calc-silicate hornfels, Twin Lakes area, central Sierra Nevada, California

Abstract In the Twin Lakes area, central Sierra Nevada, California, most contact metamorphosed marbles contain calcite + dolomite + forsterite ± diopside ± phlogopite ± tremolite, and most calc-silicate hornfelses contain calcite + diopside + wollastonite + quartz ± anorthite ± K-feldspar ± grossular ± titanite. Mineral-fluid equilibria involving calcite + dolomite + tremolite + diopside + forsterite in two marble samples and wollastonite + anorthite + quartz + grossular in three hornfels samples record P± 3 kbar and T± 630° C. Various isobaric univariant assemblages record CO₂-H₂O fluid compositions of χCO₂= 0.61–0.74 in the marbles and χCO₂= 0.11 in the hornfelses. Assuming a siliceous dolomitic limestone protolith consisting of dolomite + quartz ° Calcite ± K-feldspar ± muscovite ± rutile, all plausible prograde reaction pathways were deduced for marble and hornfels on isobaric T-XCO₂ diagrams in the model system K₂O-CaO-MgO-Al₂O₃-SiO₂-H₂O-CO₂. Progress of the prograde reactions was estimated from measured modes and mass-balance calculations. Time-integrated fluxes of reactive fluid which infiltrated samples were computed for a temperature gradient of 150 °C/km along the fluid flow path, calculated fluid compositions, and estimated reaction progress using the mass-continuity equation. Marbles and hornfelses record values in the range 0.1–3.6 × 10⁴ cm³/cm² and 4.8–12.9 × 10⁴ cm³/cm², respectively. For an estimated duration of metamorphism of 10⁵ years, average in situ metamorphic rock permeabilities, calculated from Darcy's Law, are 0.1–8 × 10^?6 D in the marbles and 10–27 × 10^?6 D in the hornfelses. Reactive metamorphic fluids flowed up-temperature, and were preferentially channellized in hornfelses relative to the marbles. These results appear to give a general characterization of hydrothermal activity during contact metamorphism of small pendants and screens (dimensions ± 1 km or less) associated with emplacement of the Sierra Nevada batholith.     

Discriminating between pore‐filling load and bed‐structure load: a new porosity‐based method,exemplified for the river Rhine

Sediments contained in the river bed do not necessarily contribute to morphological change. The finest part of the sediment mixture often fills the pores between the larger grains and can be removed without causing a drop in bed level. The discrimination between pore‐filling load and bed‐structure load, therefore, is of practical importance for morphological predictions. In this study, a new method is proposed to estimate the cut‐off grain size that forms the boundary between pore‐filling load and bed‐structure load. The method evaluates the pore structure of the river bed geometrically. Only detailed grain‐size distributions of the river bed are required as input to the method. A preliminary validation shows that the calculated porosity and cut‐off size values agree well with experimental data. Application of the new cut‐off size method to the river Rhine demonstrates that the estimated cut‐off size decreases in a downstream direction from about 2 to 0·05 mm, covariant with the downstream fining of bed sediments. Grain size fractions that are pore‐filling load in the upstream part of the river thus gradually become bed‐structure load in the downstream part. The estimated (mass) percentage of pore‐filling load in the river bed ranges from 0% in areas with a unimodal river bed, to about 22% in reaches with a bimodal sand‐gravel bed. The estimated bed porosity varies between 0·15 and 0·35, which is considerably less than the often‐used standard value of 0·40. The predicted cut‐off size between pore‐filling load and bed‐structure load (D_c,p) is fundamentally different from the cut‐off size between wash‐load and bed‐material load (D_c,w), irrespective of the method used to determine D_c,p or D_c,w. D_c,w values are in the order of 10^?1 mm and mainly dependent on the flow characteristics, whereas D_c,p values are generally much larger (about 10⁰ mm in gravel‐bed rivers) and dependent on the bed composition. Knowledge of D_c,w is important for the prediction of the total sediment transport in a river (including suspended fines that do not interact with the bed), whereas knowledge of D_c,p helps to improve morphological predictions, especially if spatial variations in D_c,p are taken into account. An alternative to using a spatially variable value of D_c,p in morphological models is to use a spatially variable bed porosity, which can also be predicted with the new method. In addition to the morphological benefits, the new method also has sedimentological applications. The possibility to determine quickly whether a sediment mixture is clast‐supported or matrix‐supported may help to better understand downstream fining trends, sediment entrainment thresholds and variations in hydraulic conductivity.     

Anhydrite pseudomorphs and the origin of stratiform Cu–Co ores in the Katangan Copperbelt (Democratic Republic of Congo)

The stratiform Cu–Co ore mineralisation in the Katangan Copperbelt consists of dispersed sulphides and sulphides in nodules and lenses, which are often pseudomorphs after evaporites. Two types of pseudomorphs can be distinguished in the nodules and lenses. In type 1 examples, dolomite precipitated first and was subsequently replaced by Cu–Co sulphides and authigenic quartz, whereas in type 2 examples, authigenic quartz and Cu–Co sulphides precipitated prior to dolomite and are coarse-grained. The sulphur isotopic composition of the copper–cobalt sulphides in the type 1 pseudomorphs is between −10.3 and 3.1‰ relative to the Vienna Canyon Diablo Troilite, indicating that the sulphide component was derived from bacterial sulphate reduction (BSR). The generation of during this process caused the precipitation and replacement of anhydrite by dolomite. A second product of BSR is the generation of H₂S, resulting in the precipitation of Cu–Co sulphides from the mineralising fluids. Initial sulphide precipitation occurred along the rim of the pseudomorphs and continued towards the core. Precipitation of authigenic quartz was most likely induced by a pH decrease during sulphide precipitation. Fluid inclusion data from quartz indicate the presence of a high-salinity (8–18 eq. wt.% NaCl) fluid, possibly derived from evaporated seawater which migrated through the deep subsurface. ⁸⁷Sr/⁸⁶Sr ratios of dolomite in type 1 nodules range between 0.71012 and 0.73576, significantly more radiogenic than the strontium isotopic composition of Neoproterozoic marine carbonates (⁸⁷Sr/⁸⁶Sr = 0.7056–0.7087). This suggests intense interaction with siliciclastic sedimentary rocks and/or the granitic basement. The low carbon isotopic composition of the dolomite in the pseudomorphs (−7.02 and −9.93‰ relative to the Vienna Pee Dee Belemnite, V-PDB) compared to the host rock dolomite (−4.90 and +1.31‰ V-PDB) resulted from the oxidation of organic matter during BSR.     

湖北徐家山锑矿床流体包裹体特征及其意义

文章利用激光拉曼光谱和显微测温学方法,对湖北徐家山锑矿床成矿期的石英、重晶石和方解石中的流体包裹体进行了研究。研究表明,这些矿物中的流体包裹体主要有纯液体包裹体和液体包裹体(气相 液相)2类,其液体包裹体的气相成分为H2O±CO2±N2;石英、重晶石和方解石的均一温度分别为134~258℃、154~259℃和145~230℃,主要集中于150~200℃;流体的盐度w(NaCleq)和密度分别集中于3%~6%和0.90~0.96g/cm3。流体包裹体资料揭示出该矿床为典型的中低温热液锑矿床,其成矿流体为中低温、低盐度、中等密度热液。结合H、O、Sr、Pb同位素等研究结果,进一步推断该成矿热液主要是经深部循环演化的大气降水。     

新疆阿尔泰蒙库铁矿床的成矿流体及成矿作用

蒙库大型铁矿床赋存于上志留统—下泥盆统康布铁堡组变质火山-沉积岩系中,容矿岩石为石榴子石矽卡岩、变粒岩、浅粒岩和大理岩。矿体总体顺层分布,空间上与矽卡岩密切相关。研究表明,矽卡岩期石榴子石以发育玻璃质熔融包裹体、流体熔融包裹体和流体包裹体为特征,晚期矽卡岩阶段矿物中发育液相包裹体,变质期矿物中主要发育液相包裹体和含子矿物包裹体。矽卡岩期熔融包裹体的均一温度为1100℃,早期矽卡岩阶段流体包裹体均一温度变化于193～499℃,在450℃、350℃和230℃出现峰值。中期矽卡岩阶段均一温度变化于236～550℃,峰值为350℃。区域变质期均一温度介于132～513℃,在350℃、230℃和190℃出现峰值。流体包裹体的盐度w(NaCleq)介于1.23%～60.31%,流体密度变化于0.60～1.16g/cm3。石榴子石、石英和方解石的δ18OSMOW变化于0.2‰～8.4‰,δ18OH2O介于-5.1‰～5.33‰,δD为-127‰～-81‰,表明矽卡岩期成矿流体主要是岩浆水,混合少量大气降水;变质期流体主要为大气降水,为混合变质水。方解石δ13CPDB变化于-6.1‰～-2.3‰,表明流体中碳来自深部或地幔。成矿时代为早泥盆世早期(略晚于404～400Ma),成矿作用与矽卡岩的退化变质作用有关。     

豫西前河构造蚀变岩型金矿成矿过程中的流体-岩石反应

前河金矿区位于华北地台南缘,赋存在中元古界熊耳群安山岩和英安岩中,矿体受断裂破碎带控制。含矿热液在迁移过程中与围岩发生了广泛的流体-岩石反应而引起热液蚀变。本区石英中有4种类型的流体包裹体,均一温度范围为145～331℃,其中含CO2包裹体的完全均一温度主要分布在中-高温区。成矿流体的密度和压力变化范围分别是0.68～0.94g/cm3和(367.01～896.55)×105Pa。金大量沉淀成矿时的流体特征为:温度213～260℃、密度0.80～0.89g/cm3和压力(502.86～710.57)×105Pa。流体相为SO42->Na >Cl->K 型,CO2/H2O比值及N2、H2S、Ar、C2H6等挥发分的含量明显增高,f(CO2)、f(H2S)、f(CH4)和Eh值增大;f(O2)、f(H2O)和pH值减小。在青磐岩化安山岩的基础上发生的流体-岩石反应是造成本矿床金沉淀成矿的最主要原因。     

Response of groundwater chemistry to water deliveries in the lower reaches of Tarim River,Northwest China

In this paper, we analysed the monitored data from nine groundwater-monitoring transects in the lower reaches of Tarim River during the five times of stream water deliveries to the river transect where the stream flow ceased. The results showed that the groundwater depth in the lower reaches of Tarim River rose from −9.30 m before the conveyances to −8.17 and −6.50 m after the first and second conveyances, −5.81 and −6.00 m after the third and fourth the conveyance, and −4.73 m after the fifth. The horizontal extent of groundwater recharge was gradually enlarged along both sides of the channel of conveyance, i.e., from 250 m in width after the first conveyance to 1,050 m away from the channel after the fourth delivery. With the rising groundwater level, the concentrations of major anions Cl⁻, SO₄²⁻ and cations Ca²⁺, Mg²⁺, Na⁺, as well as total dissolved solids (TDS) in groundwater underwent a significant change. The spatial variations in groundwater chemistry indicated that the groundwater chemistry at the transect near Daxihaizi Reservoir changed earlier than that farther from it. In the same transect, the chemical variations were earlier in the monitoring well close to watercourse than that farther away from the stream. In general, the concentration of the major ions and TDS at each monitoring well increased remarkably when the water delivery started, and decreased with the continued water delivery, and then increased once again at the end of the study period. Hence, the whole study period may be divided into three stages: the initial stage, the intermediate stage and the later stage. According to the three stages of groundwater chemistry reaction to water delivery and the relationships between groundwater chemical properties and groundwater depths, we educe that under the situation of water delivery, the optimum groundwater depth in the lower reaches of the Tarim River should be −5 m.